Silver halide emulsion containing naphthamide photographic couplers

ABSTRACT

THIS INVENTION RELATES TO COMPOUNDS USEFUL AS PHOTOGRAPHIC COUPLERS HAVING THE GENERAL FORMULA:   1-HO,2-((2-X,5-(R-Y-)PHENYL)-NH-CO-),4-Z-NAPHTHALENE   WHEREIN X IS ALKYL, Y IS EITHER CARBONYL OR SULFONYL, R IS ALKYL HAVING FROM 5 TO 20 CARBON ATOMS AND Z IS HYDROGEN OR HALOGEN. THE INVENTION ALSO RELATES TO THE USE OF THE ABOVEMENTIONED COMPOUNDS IN PHOTOGRAPHIC EMULSIONS.

July 6, 1971 uzz ETAL 3,591,384

SILVER HALIDE EMULSION CONTAINING NAPHTHAMIDE PHOTOGRAPHIC COUPLERSFiled Jan. 31, 1968 FIG.

5 0 a \CREWQ 63 mskvqmk 5 m wwm N m EUG V0 MW? 7 m 7M, E E0 mm M A m W mM 0 m United States Patent Int. Cl.- G03c 1/40 US. Cl. 96-100 6 Claims"ABSTRACT OF THE DISCLOSURE This invention relates to compounds usefulas photoand moisture and having good spectral characteristics,particularly low secondary absorptions.

It is an object of this invention to provide a new class of outstandingcyan couplers and photographic emulsions 5 incorporating such couplers.

The cyan couplers of this invention have the formula:

i Y.R wherein X is alkyl, preferably a lower alkyl (C -C Y f P couplersh e the general e m is either carbonyl or sulfonyl, R is C -C alkyl, andZ is r X hydrogen or halogen, preferably chlorine or bromine. g i r 1These couplers are easily obtained in a'very high purity by methodsdescribed later. 20 Illustrative couplers are as follows:

(|)H (EH3 i 3L3 CONH wherein X is alkyl, Y is either carbonyl orsulfonyl, R r is alkyl having from 5 to 20 carbon atoms and Z ishydrogen or halogen. The invention also relates to the use of (1) theabovementioned compounds in photographic emul- OH sions. l

V -CONH This invention relates to a class of couplers capable of formingstable cyan or blue-green dyes by color development in colorphotographic materials.

In the production of colored images by the color devel- 01 00011 23opment of silver halide emulsion layers in a multi-layer 0H CH3 filmconstruction the image formed after light exposure of the reduciblesilver salts is developed in the presence -C0NH of a coupler, i.e. acompound which reacts with the oxidation products of the color developerto form a dye. Cyan images are generally obtained by the formation of an40 indophenol dye from a l-hydroxy-Z-naphthamide coupler. S OZONE (3)One important requirement of color couplers used in 0H color photographyis the ability to resist bleeding or I I migration through and outsideof the photographic emul- OONH sion layers in which they are contained.An effective means for solving the migration problem is provided by thedispersed coupler method, in which the coupler is dissolved in highboiling organic solvents, such as tricresyl 01 3010181138 phosphate ordibutyl phthalate, and the resulting solution Table I shows someanalytical data of these illustrais intimately dispersed throughout thesilver halide emultive couplers, the analyses being made after only onecryssi on To obtain the best results in terms of the dispersiontallization of the raw reaction product. Included are their andphotographic efficiency the solution of coupler in the desirable meltingpoints. Their high degree of solubility organic solvent should be highlyconcentrated. Couplers in organic solvents normally used for dispersingcouplers which are highly soluble in or miscible with the organic in agelatin emulsion permits the use of a solvent/coupler solvent aretherefore commonly selected for use in disratio far lower than 1.0without any noticeable decrease persed coupler systems. In general,couplers having a relain yield of dye formed by normal color developmentprotively low melting point are quite soluble in such organic cedures.For example, coupler (l) can be incorporated solvents. However, it isalso desirable to select couplers into a photographic emulsion with 1part dibutyl phthalate which produce dyes having good stability tolight, heat containing 4 parts of coupler.

TABLE I OH, Melting C, percent H, percent N, percent 01, percent percentCrystal- Coupler point content lization No. F.) Found Cale. Found Cale.Found Gale. Found Cale. found solvent 1 15. 5-2192 78.46 78.39 8.28 8.113.00 3. 04 99. 27 Ethanol.

(102-104 0.) 2 149. 0-150 8 72.55 72.9 7. 25 7.3 7,16 7.17 98.81 Heptane99.41 Acetic acid. 240.8-2425 5.86 5. 98.44 Do.

-'In addition to the above-mentioned characteristics the claimedcouplers react with N,N-dialkyl-p-phenylenediamine during colordevelopment to provide dyes which are particularly stable to light, heatand moisture. For example, if one of thesecouplers is dissolved indibutyl phthalate, dispersed in a photographic emulsion, coated onto atransparent support, exposed and developed with diethyl pphenylenediamine, the resultant color shows no noticeable change ineither color density or hue after exposure to a xenon lamp for 10 hours.Coated samples prepared insimilar manner were exposed through a scale ofdecreasing densities, i.e. grey scale, and developed in color developerwith. excellent sensitometric results, even after storage for 2 hours at'a temperature of 194.0 F.

(90 C.) and a relative humidity of 75%. In FIG. 1

curve A is the sensitometric curve '(read in red light) for coupler (1)and curve B is the sensitometric curve for coupler (1) after 24 hoursstorage under the abovementioned conditions. These curves show theexcellent stability of dyes prepared from the couplers of thisinvention. The spectral absorption of the cyan dyes obtained from thesecouplers and N,N-dialkyl-p-phenylenediamine developers make thenparticularly suitable for preparing color negative materials.Furthermore, they have a low absorption in the green portion of thespectrum, which is very desirable. In FIG. 2 an illustrative comparisonof the spectral absorption of N,N-diethyl-p-phenylenediamine developedcouplers in dibutyl phthalate, absorption curve A being that ofabov'ementioned coupler (3) and absorption curve B being that of acoupler of the formula:

The coupler of curve B is a known coupler having some struturalsimilarity to the couplers of this invention. From a comparison ofcurves A and B it is apparent that curve A represents lower absorptionin the 500 and 600 millimicron region than curve B.

The couplers of the present invention can be prepared by reacting thesuitable amines with 1-hydroxy-2-naphthoic acid or1-hydroxy-4-halo-2-naphthoic acid derivatives, such as their phenylesters. In particular, the preparations of some couplers of said classwere carried out in the following; way:

(a) PREPARATION OF 4-METHYLLAURO- PHENONE 1 a Into a 500 ml. flaskcontaining a suspension of 59" g. of AlCl in 168 ml. of dry toluene,69.2 g. of lauroyl chloride were rather quickly introduced. Thetemperature rose to 14O.0 F. (60 C.). The mixture was kept understirring at a temperature of 176.0 F. (80 C.) for 22 hours, then waspoured with vigorous stirring into 1000 ml. of water and 66.5 ml. ofconcentrated hydrochloric acid. After about one hour the organic layerwas removed and washed, first with a 1% Na CO solution and then withwater. The toluene solution was then dried with calcium chloride, andthe solvent was removed under vacuum. The residue, consisting of areadily solidifying oil, was crystallized from ethanol. Yield: 58.8 g.(67% M- PF. l15,-.5,"v .F., (4.5f46.5 ,.C.).

Analysis-Calculated for C H O (percent): C, 83.57;

H, 10.94. Found (percent): C, 83.27; H, 10.94.

(b). PREPARATION OF 3-NITRO-4-METHYL- LAUROPI-IENONE In a beakerprovided with stirrer and thermometer, was placed 190 m1. of HNO(d=1.52) and then 69.9 g. of 4-methyllaurophenone was added inincrements. The operation was carried out as rapidly as possible whilemaintaining the reaction temperature below 44.6" F.

(7 C.). After completion, of the ketone addition the the mixture wasadded dropwise into one liter of ice water. The precipitated product wasfiltered off and thoroughly washed with water, then allowed to dry inthe air. By crystallization from methanol 86.4 g. of the nitroderivative with M.P.: l22.0-123.8 F. (5051 C.) was obtained.

(c) PREPARATION OF 3-AMINO-4-METI-IYIIQ LAUROPHENONE 56.4 g. of3-nitro-4-methyllaurophenone was dissolved in a boiling mixture of 530ml. of 90% acetic acid and 260 ml. of ethanol. Then 106 g. of ironpowder was slowly added. After completion of the addition boiling wascontinued for about 30 minutes, after which the ferrous slime .was hotfiltered and the filtrate was poured with stirring into 17.5 ml. ofwater. The amine which separated was filtered oil and thoroughly washedwith water. Yield of raw product: 48.6 g. By crystallizing the rawproduct from 485 ml. of ethanoland decolorizing with charcoal, 41.5 g.(81.2%) of product having a M.P. of 167.0-l70.6 F. (77 C.) was obtained.

Analysis.Calculated for C I-1 1810 (percent): N, 4.84. Found (percent):N, 4.65; --NH content, 100.00.

((1) PREPARATION OF l-HYDROXY-2-(2'-METHYL- 5-LAUROYL) NAPHTHANILIDE(COUPLER- 1) In a Claisen flask arranged for distillation under vacuum amixture of 63.6 g. of 3-amino-4-methyllaurophenone and 63.6 g. of phenyl1-hydroxy-2-naphthorate was melted. At this point vacuum was applied inorder to remove the phenol which was liberated as the reactioncontinued. After about half an hour the amount of distilled phenol was22 g. (theory: 22.6 g.). The residue was crystallized from ethanol.Yield of coupler: 91.5 g.

(e) PREPARATION OF l-HYDROXY-4-CHLORO-2- 2 METHYL 5LAUROYL)NAPHTHANILIDE (COUPLER 2) By working in the same way asdescribed for the coupler 1 and employing an equivalent amount of phenyl1-hydroxy-4-chloro-Z-naphthoate instead of phenyl l-hydroxy-2-naphthoate86 g. of coupler was obtained after crystallization from heptane.

(f) PREPARATION OF p-TOLYL CETYL S'ULFONE (g) PREPARATION OF3-NITRO-4-METHYL- PHENYL CETYL SULFON'E It was obtained in a way similarto the 3-nitro-4-methyllaurophenone by using 112 ml. of fuming HNO for-56.8 g. of-p-tolyl-cetyl-"sulfone. Yield? 55.2 g. (from ethanol) M.P.:161.6163.4 F. (7273 C.).

(h) PREPARATION OF 3-AMINO-4-METHYL- PHENYL ACETYL SULFONE (i)PREPARATION OF l-HYDROXY-2-(2'-METHYL- 5-CETYLSULFONYL) NAPHTHANILIDE(COU- PLER 3) By following the same procedure as with coupler (1), 47.3g. of 3-amino-4-methylphenyl cetyl sulfone was reacted with 34.7 g. ofphenyl l-hydroxy-Z-naphthoate. 59.2 g. of coupler (3) was obtained.

(l) PREPARATION OF l-HYDROXY-4CHLORO-2- (2'-METHYL-5 -CETYLSULFONYL)-NAPHTHANI LIDE (COUPLER 4) The product was obtained by proceduressimilar to those used in the preceding examples from 39.5 g. of3-amino-4- methylphenyl cetyl sulfone and 32.8 g. of phenyll-hydroxy-4-chloro-2-naphthoate. Yield was 43 grams.

(k) PREPARATION OF 1-HYDROXY-2-(2'-METH- YL-S -DECYLSULFONYL)NAPHTHANILIDE Obtained by a synthesis similar to that of the coupler(3), using decyl bromide instead of cetyl bromide.

The properties of the intermediates are the following:

The coupled was obtained by the reaction of the raw amine with phenyll-hydroxy-Z-naphthoate and, after crystallization from ethanol, the M.P.was 273.2-277.5 F. (l34-l36.5 C.).

A nalysisSOH/c011tent=96.87%

Example 1 2 grams of coupler (1) was dissolved in a mixture consistingof 0.5 ml. of dibutyl phthalate and 12 ml. of ethyl acetate by heatingon a boiling water bath. The resulting clear solution was poured into 40ml. of 4% gelatin containing 4 ml. of sodium tetradecyl sulfatesolution. At a temperature of about 104.0 F. (40 C.) the mixture wasdispersed in a homogcnizer. The dispersion thus obtained was added to200 g. of silver halide photographic emulsion sensitized to red light.The thus modified emulsion was spread on a transparent support, driedand exposed through an original. By chromogenic development in aN,N-diethyl-p-phenylenediamine developer, a negative blue-green coloredimage was obtained. The stable blue-green dye forming the image had anabsorption peak at 688 m Example 2 A dispersion of the followingformulation:

Coupler (3)2 grams Dibutyl phthalate-4 ml.

Ethyl acetate12 m1.

4% gelatin40 m1.

10% sodium tetradecyl sulfate solution-4 ml.

was added to 200 grams of a negative-type silver halide emulsion,sensitized to red light. The thus modified emulsion was spread onto atransparent support and dried. The photosensitive material thus obtainedwas exposed through an original and developed in a color developer ofthe following formulation:

Grams Hydroxylamine hydrochloride 1 Diethyl-p-phenylenediamine sulfate2.8 Sodium tripolyphosphate 2 Anhydrous sodium carbonate 65 Anhydroussodium sulfite 25 Potassium bromide 1.2

Water to make 1000 ml. (pH 10.88.11 with NaOH).

After the usual steps of bleaching, fixing and washing, a blue-greencolored negative image of the original was obtained. The absorptioncurve of the blue-green dye forming the image is the same as curve A inFIG. 2. The absoprtion peak of the dye lies at 697702 III-,u.

Various other embodiments of the present invention will be apparent tothose skilled in the art without departing from the scope thereof.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A silver halide photographic emulsion containing dispersed therein atleast one compound of the general formula:

wherein X is lower alkyl, Y is carbonyl or sulfonyl, R is an alkyl grouphaving from 5 to 20 carbon atoms, and Z is hydrogen or halogen.

2. A photographic element having at least one layer comprising theemulsion of claimv 1.

3. The emulsion of claim 1 wherein said compound has the formula 4. Theemulsion of claim 1 wherein said compound has the formula OH CH3 CONH C1OCnHza 5. The emulsion of claim 1 wherein said compound has the formula(IJH $113 Q C O U l SOzCroHas 6. The emulsion of claim 1 wherein saidcompound has the formula References Cited UNITED STATES PATENTS3,459,552 8/1969 Yoshida et a1. 96-100 J. TRAVIS BROWN, Primary ExaminerUS. Cl. X.R. 260-559 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3.591.38" Dated Jul; 6 1971 lnventofls) AlbertoGuzzi and Remo Magagnoli It is certified that error appears in theabove-identified patent and that. said Letters Patent are herebycorrected as shown below:

Column 3, line 1 "2 hours" should read 24 hours Column 4, line 33,"l-hydroaw-iQ-naphthorate" should read l-hydroxy2-naphthoate Column 1%,line +0, "2-methyl" (etc.) should read (2'-methyl (etc.);

Column line 70, "acetyl" should read cetyl Column 5, line 31, "coupled",should read coupler Column 6, line 15, OH

/I CONH Signed and sealed this 2 6th day of Sept ember l9 7 2 SEAL)Arrest;

'l EDWARD M VTTETCHER'L JR ROBERT GOTTSCHALK A? t est i n 0F f' i uerComml' ssioner of Patent 5

